Lithium intercalated nanocrystal anodes

ABSTRACT

A prelithiated anode for use in a lithium ion battery is composed of an electrode substrate, a paste distributed on the electrode substrate and comprising a plurality of Si, Ge, or SiGe nanocrystals intercalated with lithium ions, and a binder mixed with the paste to adhere the paste to the electrode substrate. The lithiated anode paste may be formed by an electrodeposition process or an electrolytic process.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national phase application under 35 U.S.C. § 371of International Application No. PCT/US2015/031262 filed on 15 May 2015entitled “Lithium Intercalated Nanocrystal Anodes,” which claims thebenefit of priority pursuant to 35 U.S.C. § 119(e) of U.S. provisionalapplication No. 61/993,840 filed 15 May 2014 entitled “Method forproducing high energy capacity nanocrystal based anodes for lithium ionbatteries,” U.S. provisional application No. 61/993,870 filed 15 May2014 entitled “Method for producing sulfur charged carbon nano tubecathodes for lithium ion batteries,” and U.S. provisional applicationNo. 61/993,779 filed 15 May 2014 entitled “Methods and systems for thesynthesis of nano particles including strained nano particles,” each ofwhich is hereby incorporated herein by reference in its entirety.

TECHNICAL FIELD

The technology described herein relates to the design and manufacture ofanodes for lithium ion batteries, and particularly to high energycapacity, prelithiated anodes of silicon and germanium nanocrystals.

BACKGROUND

Lithium ion batteries have been proven to offer higher energy and powerdensity, a wider range of operating temperatures, and excellent cycleand calendar life when compared to other battery chemistries. Continueddemand for various portable electronics, such as electric hand and powertools, as well as high power applications of electric basedtransportation, continues to direct research to focus on lower costmaterials without compromise of reliability and life of lithium ionbatteries.

The information included in this Background section of thespecification, including any references cited herein and any descriptionor discussion thereof, is included for technical reference purposes onlyand is not to be regarded subject matter by which the scope of theinvention as defined in the claims is to be bound.

SUMMARY

In one exemplary implementation, a prelithiated anode for use in alithium ion battery is composed of an electrode substrate, a pastedistributed on the electrode substrate and comprising a plurality of Si,Ge, or SiGe nanocrystals intercalated with lithium ions, and a bindermixed with the paste to adhere the paste to the electrode substrate. Thenanocrystals may have a multimodal size distribution, but are highlyspherical in form and may be below threshold sizes depending upon thetype of nanocrystal in order to maximize the intercalation of lithiumand discharge and recharge cycles.

In another exemplary implementation, a method for manufacturingprelithiated anodes for use in a lithium ion battery may include anumber of steps. Initially, Si, Ge, or SiGe nanocrystals may be mixedwithin a fluid containing a lithium electrolyte. A first lithium metalelectrode may be placed within the fluid mixture. A second lithium metalelectrode may be placed within the fluid mixture spatially separatedfrom the first lithium metal electrode. A voltage may be applied acrossthe electrodes such that the first lithium metal electrode is positivelycharged. A paste of lithium-intercalated Si, Ge, or SiGe nanocrystals isallowed to form on the first lithium metal electrode. The paste may beremoved from the first lithium metal electrode and mixed with a binder.The paste and binder mixture may be deposited on a conductive anodesubstrate. The binder may be cured to adhere the paste to the conductiveanode substrate.

In a further exemplary implementation, a method for manufacturingprelithiated anodes for use in a lithium ion battery may include anumber of steps. Initially, Si, Ge, or SiGe nanocrystals may be mixedwithin an ionic fluid, a nonaqueous solvent, or a mixture of both. Alithium metal anode electrode may be placed within the mixture. Acathode electrode may be placed\ within the mixture spatially separatedfrom the lithium metal anode electrode. A voltage may be applied acrossthe electrodes such that the lithium metal anode electrode is positivelycharged. A paste of lithium-intercalated Si, Ge, or SiGe nanocrystals isallowed to form on the lithium metal anode electrode. The paste may beremoved from the lithium metal anode electrode and mixed with a binder.The paste and binder mixture may be deposited on a conductive anodesubstrate. The binder may be cured to adhere the paste to the conductiveanode substrate.

This Summary is provided to introduce a selection of concepts in asimplified form that are further described below in the DetailedDescription. This Summary is not intended to identify key features oressential features of the claimed subject matter, nor is it intended tobe used to limit the scope of the claimed subject matter. A moreextensive presentation of features, details, utilities, and advantagesof the present invention as defined in the claims is provided in thefollowing written description of various embodiments and implementationsand illustrated in the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow diagram depicting operational steps for producingsulfur charged carbon nanotubes.

FIG. 2 is a flow diagram depicting operational steps for producing asulfur-charged carbon nanotube cathode for use in a lithium ion battery.

FIG. 3 is a magnified view of sulfur-charged carbon nanotubes on acathode according to the embodiment of FIG. 2.

FIG. 4 is a magnified view of a sulfur-charged carbon nanotube inaccordance with the embodiment of FIG. 3.

FIG. 5 is a schematic diagram of a half-cell incorporating a sulfurcharged carbon nanotube cathode.

FIG. 6 is a flow diagram of a process for manufacturing a half-cellincorporating a sulfur-charged carbon nanotube cathode.

FIG. 7A is a magnified image of a collection of pristine germaniumnanocrystals

FIG. 7B is a magnified image of a collection of germanium nanocrystalspost intercalation with lithium atoms exhibiting expansion and ananopore morphology.

FIG. 7C is a magnified micrograph image of a group of germaniumnanocrystals.

FIG. 8 is a magnified micrograph image of a germanium nanocrystaldeposition having a bimodal distribution of nanocrystals of twodifferent diameters.

FIG. 9 is a flow diagram of a process for manufacturing a high energycapacity anode for lithium ion batteries via electrochemical supersaturation of lithium into silicon, germanium, and/or silicon-germaniumalloy nanoparticles.

FIG. 10 is a flow diagram of a process for manufacturing a high energycapacity anode for lithium ion batteries via electrolytic supersaturation of lithium into silicon, germanium, and/or silicon-germaniumalloy nanoparticles.

FIG. 11 is a graphic plot of sequential charge/discharge cycles ofbattery having a prelithiated germanium nanocrystal anode in units ofvoltage vs. time.

FIG. 12 is a schematic diagram in an exploded view of a half-cellincorporating a high energy capacity lithium-intercalated germaniumnanocrystal anode.

FIG. 13 is a flow diagram of a process for manufacturing a half-cellincorporating a high energy capacity lithium-intercalated germaniumnanocrystal anode.

FIG. 14 is a graphic plot of sequential charge/discharge cycles of aprelithiated germanium nanocrystal anode half-cell.

FIG. 15 is a schematic diagram of a battery cell incorporating a sulfurcharged carbon nanotube cathode and a high energy capacitylithium-intercalated germanium nanocrystal anode.

FIG. 16 is a flow diagram of a process for manufacturing a battery cellincorporating a sulfur charged carbon nanotube cathode and a high energycapacity lithium-intercalated germanium nanocrystal anode.

FIG. 17 is a schematic diagram of a system for producing nanoparticles.

FIG. 18 is a schematic diagram of an alternate system for producingnanoparticles.

FIG. 19 is a process chart illustrating the fabrication of one or moredevices that comprise nanoparticles.

DETAILED DESCRIPTION

High-power and energy-dense lithium-ion batteries are desirable forportable electronics, electric vehicles, and peak power storage forincreased life, range, and capacity. Improvements to lithium-ioncathodes and anodes are sought to increase storage capacity and thenumber of recharge cycles before structural breakdown.

Sulfur-Charged Carbon Nanotube Cathodes

The lithium-sulfur (Li—S) cell has become an attractive option forcathode architecture because of the high theoretical specific energydensity of about 2600 Wh/kg (1672 mAh/g), assuming complete reaction toLi2S. Additionally, advancing lithium-sulfur energy (Li—S) storagecyclability (i.e., the number of times a battery can be recharged beforedropping below 80% of its initial capacity) has the potential tosubstantially improve battery technology because of a high theoreticalenergy density (1672 mA h g⁻¹) of Li—S architecture for use inlithium-ion batteries. In addition to the high capacity, using sulfur asa cathode material has the advantages of high natural abundance and lowcost while also being ecofriendly. In traditional Li—S architectures,low cyclability prevents the technology from being a commercially viableproduct. Recent advances in material technologies and applications withrespect to electric vehicles have spurned new interest in Li—S systems.

Traditional Li—S battery systems have several drawbacks. First,elemental sulfur has poor electrical conductivity (5.0 e⁻¹⁴ S*cm⁻¹).Second, polysulfides (Li₂S_(n)) may branch into the electrolyte solutionbetween the anode and the cathode during cycling. If the polysulfidescross the separator between the anode and cathode and react with thelithium negative electrode, the amount of active sulfur in the cathodeis reduced and subsequently cycling efficiency decreases with eachcycle. Ultimately, the reduction in sulfur can cause the battery toshort. Continuous reduction of the Li₂S_(n) polysulfides by the Lianodes prevents the redox reaction back to elemental sulfur at thecathode side upon charging. This cyclic process is known as the“shuttle” phenomenon of Li—S sulfur systems and leads to a limitedcapacity much lower than the theoretical value of sulfur electrodes.Third, production of Li—S cathodes can result in unusable byproductsthat increase waste.

Embodiments described herein provide methods for creating sulfur chargedcarbon nanotubes, which may be used in Li—S battery cathodes. Asdescribed in further detail below, encapsulating sublimed sulfur incarbon nanotubes may compensate for the poor electrical conductivity ofsulfur without sacrificing the increased capacity of sulfur cathodes.Additionally, the carbon nanotubes allow for polysulfides to form,providing a diffusion path for lithium ions, while reducing the abilityof the polysulfides to branch into the electrolyte solution toward theanode and short the battery. Embodiments described herein enable, amongother things, low cost, high yield, and scalable methods of producingsulfur charged carbon nanotube cathodes for use in Li—S batteries

Turning now to the figures, FIG. 1 is a method, generally designated100, depicting operational steps for producing sulfur charged carbonnanotubes. In operation 102, sulfur is dissolved in a solvent. Invarious embodiments, the sulfur may be sublimed elemental sulfur. Thesolvent may be any suitable solvent. In one embodiment, the solvent iscarbon disulfide (CS₂). In various embodiments, the amount of sulfur maybe determined based on the amount of solvent and the amount of sulfurcharged carbon nanotubes desired. For example, the sulfur may beapproximately 50% wt-98% wt of the combined sulfur-nanotube mixture. Incertain embodiments, one gram of sublimed sulfur may be added for everyfive ml of CS₂. Those skilled in the art will appreciate that differentcombinations are possible so long as the sulfur is completely dissolvedin the solvent. The sulfur and solvent may be stirred, sonicated, and/orheated in order to increase the solubility of the sulfur in the solventand/or ensure even dispersion of the sulfur in the solution. In certainembodiments, the solution may be heated to 32°-33° C. while stirring.

In operation 104, carbon nanotubes are added to the sulfur solution. Thequantity of carbon nanotubes may be depend on the desired finalcomposition of the sulfur charged carbon nanotubes. In variousembodiments, the amount of nanotubes may be approximately 2% wt-50% wtof the combined sulfur-nanotube mixture. In various embodiments, thecarbon nanotubes may be any of single wall, soluble wall, and/ormultiwall nanotubes. In some embodiments, the nanotubes are less than 10nm in diameter. In some embodiments, the nanotubes are less than 5 μm inlength. In other embodiments, the nanotubes are less than 3 μm inlength. In various embodiments, reducing the length of the nanotubes canreduce bundling of the nanotubes and provide more even coatings whenapplied to an electrode material. The type of carbon nanotube may beselected based on the desired electrical properties of the resultingcathode. The mixture containing the sulfur, solvent, and nanotubes maybe sonicated and/or stirred to evenly disperse the carbon nanotubes inthe mixture. By first dissolving the sulfur in the solvent, the carbonnanotubes are filled with sulfur by nanocapillary action. Capillaryaction is the ability of a liquid to fill a narrow space without (or incontravention of) external forces working on the liquid (e.g., gravity).In small diameter tubes, such as carbon nanotubes, capillary actionresults from intermolecular forces within the liquid (e.g. surfacetension) and adhesive forces between the liquid and the nanotube.

In operation 106, a polar protic solvent is added while heating thesulfur-nanotube mixture. In various embodiments, the polar proticsolvent may be methanol, isopropyl alcohol, ethanol, and distilledwater. In certain embodiments, the polar protic solvent may be added ata controlled rate (e.g., drops at a rate of 1 ml/min). Thesulfur-nanotube mixture may be stirred and/or heated while adding thepolar protic solvent. For example, the mixture may be heated to atemperature of 33°-35° C. By varying the rate at which the polar proticsolvent is added to the solution, the size of sulfur particles may becontrolled. Additionally, the polar protic solvent may facilitate a pibond between sulfur particles and the carbon nanotubes, allowing sulfurto bond to the outside of the nanotubes in addition to filling thenanotubes via the nanocapillary action described above. By attachingsulfur to the outside of the carbon nanotubes, the cyclability andcapacity of a resulting Li—S battery may be increased.

In operation 108, the solvent (i.e., the solvent described above withrespect to operation 102) is removed to isolate the sulfur-carbonnanotube product. The solvent may be removed by any means that does notdamage the sulfur-carbon nanotube product. In certain embodiments, thesulfur-carbon nanotube mixture may be heated (e.g., to 35° C.) toevaporate a portion of the solvent until a moist mixture remains. Theremaining moist mixture may be spread on a tray to air dry and allow anyremaining solvent to evaporate. A two-stage drying process, as describedherein, may help the resulting sulfur-carbon nanotube product maintain aparticulate form, which can facilitate later processing steps. Incertain embodiments, the resulting sulfur-carbon nanotube product may beground into fine particles to facilitate later processing steps. Invarious embodiments, the evaporated solvent may be captured and reusedin future processes, thereby reducing unusable byproducts produced infabricating sulfur charged nanotubes. The embodiment of FIG. 1 producesparticulate sulfur-charged nanotubes with sulfur filling the carbonnanotubes and attached to the exterior of the nanotubes. The structureof the resulting sulfur charged carbon nanotubes is described in furtherdetail below with respect to FIGS. 3 and 4.

FIG. 2 is a method, generally designated 200, depicting operationalsteps for producing a sulfur charged carbon nanotube cathode for use ina lithium ion battery. The embodiment of FIG. 2 provides a process bywhich Li—S cathodes may be produced using sulfur charged carbonnanotubes, such as those described above with respect to FIG. 1.

In operation 202, a slurry is prepared with a sulfur charged carbonnanotubes. The slurry may include, for example, a binding agent, such aspoly(acrylonitrile-methyl methacrylate), a conductive carbon additive,and a solvent, such as N-methylpyrrolidinone. The binding agent mayadhere the sulfur charged carbon nanotubes to one another. Theconductive carbon additive may increase the conductivity of theresulting cathode. The solvent may be used to achieve a desirableviscosity of the slurry to ease the manufacturing product and ensure aneven coating of the sulfur charged carbon nanotubes on the cathode.

In operation 204, an aluminum electrode is coated with the slurry. Invarious embodiments, the aluminum electrode may be a sheet of aluminumfoil. The slurry coating may have a thickness of approximately 20-50 μm.The binding agent described above with respect to operation 202 may alsoact to bind the slurry to the aluminum electrode. The coated electrodemay optionally be compressed using a roll press to achieve a desiredthickness of the slurry coating. Those skilled in the art willappreciate that varying the thickness of the slurry, and, therefore, thelayer of sulfur charged carbon nanotubes, the properties of theresulting cathode may be adjusted. For example, increasing the thicknessof the sulfur charged carbon nanotubes may increase the amount oflithium that may penetrate the cathode. In operation 206, the solvent(i.e., the solvent added in operation 202) is evaporated from thecathode. The solvent may be evaporated using any appropriate mechanism.In one embodiment, the aluminum electrode with slurry coating are placedin an oven and heated to a temperature of approximately 60° C. for asufficient amount of time to evaporate substantially all of the solventfrom the slurry. In operation 208, cathodes may be cut to shape from thesulfur charged carbon nanotube coated aluminum electrode. For example,cathodes may be cut to shape for use in button (coin) cells, pouchcells, etc.

The cathodes produced according to the method of FIG. 2 may be used in aLi—S battery having a silicon and/or germanium anode and an electrolyteto facilitate lithium shuttling. The electrolyte may include Lithiumnitrate (LiNO₃, N-Diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide (DEMMOX), dimethyl ether (DME) and1,3-dioxolane (DOL). For example, the electrolyte may include 0.25 E³mol g⁻¹ of LiNO₃ (LiNO₃=68.95 g mol⁻¹), 0.25 E³ mol g⁻¹ of DEMMOX(DEMMOX=466.4 g mol⁻¹), and a 1:1 (wt.) mixture of DME and DOL.

FIG. 3 is a sulfur charged carbon nanotube cathode, generally designated300, according to the embodiment of FIG. 2. The cathode 300 may includea plurality of sulfur charged carbon nanotubes 302. In variousembodiments, the sulfur charged carbon nanotubes may coat an electrodematerial, such as aluminum in a substantially even layer of betweenapproximately 20-50 μm. The sulfur charged carbon nanotubes provide acathode with the energy density of a Li—S battery, while containing thesulfur particles and preventing polysulfides from bridging the gapbetween the cathode and anode to short the battery.

FIG. 4 depicts the sulfur charged carbon nanotube 302. The sulfurcharged carbon nanotube 302 includes a carbon nanotube 402 and aplurality of sulfur particles 404 attached to the outside of the carbonnanotube 402. In various embodiments, the carbon nanotube 402 may alsobe filled with sulfur particles 404. As discussed above with respect toFIG. 1, the size of the sulfur particles may be controlled based on therate at which the polar protic solvent is added to the sulfur-carbonnanotube mixture. In the depicted embodiment, the sulfur particles areapproximately 30-35 nm in diameter, and the carbon nanotube 402 chargedwith internal sulfur particles is approximately 45-50 nm in diameter.Those skilled in the art will appreciate that other sizes of sulfurparticles 404 and carbon nanotubes 402 are possible. In variousembodiments, the carbon nanotube 402 may be porous (e.g., the sulfur inthe carbon nanotubes stretches the carbon bonds creating “holes” in thecarbon nanotubes), allowing for Li-ion diffusion duringcharging/discharging cycles.

Turning now to FIGS. 5 and 6, FIG. 5 is a schematic view of a half-cellcathode, generally designated 500, for use in a coin cell. FIG. 6 is amethod, generally designated 600 for assembling a half-cell cathode inaccordance with the embodiment of FIG. 5. The half-cell cathode mayinclude a cell base 502, a sulfur charged carbon nanotube cathode 504,one or more separators 506 a/b, lithium foil 508, one or more spacers510 a/b, a biasing device 512, and a cell cover 514.

In step 602, an electrolyte 516 a is provided to the cell base 502. Theelectrolyte may be, for example, 0.25 E⁻³ mol g⁻¹ of LiNO₃ (LiNO₃=68.95g mol⁻¹), 0.25 E⁻³ mol g⁻¹ of DEMMOX (DEMMOX=466.4 g mol⁻¹), and a 1:1(wt.) mixture of DME and DOL. In one embodiment, 25 μL of theelectrolyte 516 a is provided to the center of the cell base 502. Instep 604, the sulfur charged carbon nanotube cathode 504 is placed intothe electrolyte 516 a. In various embodiments, the cathode is placedwith the aluminum contact of the cathode 504 toward the cell base 502and the sulfur charged carbon nanotube coated side away from the cellbase 502. In step 606, additional electrolyte 516 b is provided on topof the sulfur charged carbon nanotube side of the cathode 504. In oneembodiment 25 μL of electrolyte 516 b is provided on top of the cathode504.

In step 608, a first separator 506 a is placed on top of the electrolytesolution and the cathode 504. In various embodiments, the firstseparator 506 a may have a diameter commensurate with the diameter ofthe cathode 504. In certain embodiments, the first separator 506 a maybe a 19 mm polypropylene separator. In step 610, additional electrolyte516 c is provided on top of the first separator 506 a. In one embodiment25 μL of electrolyte 516 c is provided on top of the first separator 506a. In step 612, a second separator 506 b is placed on top of theelectrolyte solution 516 c and the first separator 506 a. In variousembodiments, the second separator 506 b may have a diameter commensuratewith the diameter of the first separator 506 a. In certain embodiments,the second separator 506 b may be a 19 mm polypropylene separator. Instep 614, additional electrolyte 516 d is provided on top of the secondseparator 506 b. In one embodiment 25 μL of electrolyte 516 d isprovided on top of the second separator 506 b.

In step 616, a disc of lithium foil 508, that is at least as large asthe cathode diameter, is centered and placed on the electrolyte 516 d onthe second separator 506 b. In various embodiments, the disc of lithiumfoil 508 may completely cover the cathode 504. In step 618, the one ormore spacers 510 a/b are placed on top of the lithium foil 508. Invarious embodiments, the spacers 510 a/b may be stainless steel spacers.In various embodiments, two spacers 510 a/b are placed on the lithiumfoil 508. In step 620, the biasing device 512 is placed on top of thespacers 510 a/b. In various embodiments, the biasing device 512 may be aspring washer. In other embodiments, the biasing device 512 may be anyother type of biasing device that does not interfere with the electricalproperties of the half-cell cathode 500. In step 622, the cell cover 514is placed over the cell base 502 to enclose the contents of thehalf-cell cathode 500. In various embodiments, enclosing the half-cellcathode 500 may cause electrolyte to leak from the half-cell cathode500. Any electrolyte may be removed from the outside of the half-cellcathode 500. In step 624, the cell cover 514 and the cell base 502 aresealed together to create a complete half-cell cathode 500. Thehalf-cell cathode 500 may be used to make a full coin cell as describedin further detail below with respect to FIGS. 15 and 16.

Lithium Ion-Intercalated Nanocrystal Anodes

Silicon and germanium crystals can theoretically accommodate largenumbers of lithium ions. The atomic ratio of Li atoms that can beutilized by Si or Ge atoms is 4.4:1. (or 22 Li:5 Si or Ge). Lithium ionsare small enough to fit in between the spaces of the atoms making up asilicon or germanium crystal lattice. Further, germanium is inherentlyable to accept lithium ions at a faster rate than other proposed anodematerials this has been empirically verified with test data. Lithium-iondiffusivity into Ge is 400 times faster than silicon and nearly 1000times faster than standard Li-ion technology.

FIG. 7A is a micrograph of a group of germanium nanocrystals 702 in apure state. A further magnified image of pure germanium nanocrystals isshown in FIG. 7B. The general form is highly spherical, indicating ahigh quality, uniform crystal formation conducive to maximizing thediffusive packing of lithium ions. Further, the surface morphologyindicates a number of distended protrusions 706 on each of thenanocrystals 704. This morphology translates into a significantly largersurface area for germanium nanocrystals as compared to silicon or othersimilar nanoscale crystal structures. The greater surface area isadvantageous to promoting more rapid diffusion of lithium ions into thecrystal lattice during recharge cycles. In fact, the conductivity of Geis 10,000 times higher than that of Si, and the diffusivity of Li ion inGe is 400 times faster than that of Si at room temperature, i.e., therecharge rate for Ge is 400 times faster than the recharge rate for Si.

FIG. 7C depicts a micrograph of group of lithiated germaniumnanocrystals 708 similar in scale to the pure nanocrystals 702 of FIG.7A. Comparison of the morphology of the pure nanocrystals 702 to thelithiated nanocrystals 708 indicates the expansion of the crystallattice to accept the high ratio of lithium ions. In particular, thelithiated germanium nanocrystals 708 exhibit a nanoporous structurecaused by the expansion of the nanocrystal lattice to accommodate thelithium ion intercalation. For high quality (spherically uniform) Genanocrystals, the expansion is isotropic, which minimizes strain on thecrystal lattice structure and allows for very high cycle rates andminimizes irreversible capacity loss. Conversely, large nanocrystals ofsilicon typically expand anisotropically and therefore are subject torapid capacity loss after only several cycles. However, if the Sinanocrystals are formed small enough (i.e., <100 nm and preferably <50nm) the crystal structure is more uniform and expansion behaves moreisotropically, causing less stress on the nanocrystal structure and thusincreasing the cycling capacity.

In a lithium ion battery, the lithium source needs to be in the anode orthe cathode; it cannot be in both. A charged battery contains all of thelithium in the anode. Commercially available batteries typically haveall of the lithium stored in the cathode in the form of a lithium metaloxide, i.e., lithium cobalt oxide or lithium manganese oxide or similar.At the end of the manufacturing process for Li-ion batteries, all of thebatteries have to be cycled at least once for the lithium to be insertedinto the anode so that the battery is already charged when a consumerpurchases it in a store. Lithium-metal-oxide cathodes have very limitedcapacity, on the order of 200-300 mAh/g at best.

If an anode, such as germanium, has an energy capacity of 1000 mAh/g, itcannot be effectively paired with commercially available cathodes.Because of the diffusion limits of lithium, one cannot simply add 4-5times as much cathode material to compensate for an equal volume ofanode material. In view of this dilemma, the present disclosuredescribes cost effective processes for the creation prelithiated, highenergy density anode materials for pairing with practical and low costcathode materials (e.g., sulfur) that will readily accept the lithiumstored in the anode. The anode of the full battery cell thus has lithiumalready combined/contained within the silicon or germanium nanocrystals,alleviating the need for a lithium compound cathode and an initial cycleto charge the battery for first use.

In exemplary embodiments, the anodes described herein may comprisenanocrystal (“NC”) structures of silicon (Si), germanium (Ge), orsilicon-germanium (SiGe) described herein intercalated with lithium ions(Li+) (sometimes abbreviated herein “Li—SiNC,” “Li—GeNC,” and“Li—SiGeNC,” respectively), and any combination thereof. As used herein,the terms “intercalation” or “diffusion” or “alloy” when referring tolithium intercalation into SiNC, GeNC, and/or SiGeNC as described hereinrefers to both intercalation into the crystal lattice of discretenanocrystals and intercalation between nanocrystals. These lithiatednanocrystals are then bound to a conductive substrate to form astructurally viable anode. In the exemplary anode structures andmanufacturing processes described herein, the nanocrystals need to be of“high quality” in order to achieve the significant anode lithiationresults disclosed herein. High quality in the case of Si and Genanocrystals for use in lithium-ion battery anodes means below that Sinanocrystals have diameters of less than 150 nm and are substantiallyspherical in shape and that Ge nanocrystals have diameters less than 500nm and are substantially spherical in shape. The smaller the diameter ofthe nanocrystal, the greater the packing factor in the film, thusresulting in greater energy density. A higher packing factor can beachieved with bimodal and trimodal distributions e.g., 50 nm, 17 nm, 6.5nm nanocrystal size distributions.

In some embodiments, cells, batteries, and similar devices describedherein may comprise unstrained SiGeNC and/or GeNC. In some embodiments,the batteries and similar devices described herein may comprise strainedSiGeNC and/or strained GeNC. As used herein, the terms “strained SiGeNC”and “strained GeNC” refers to SiGeNC and/or GeNC having a strainedcrystal structure, which is marked by a shift in a crystal plane whenanalyzed by x-ray diffraction. Strained SiGeNC and GeNC referencedherein may, in some embodiments, have a 20 value for the (111) crystalplane shifted relative the (111) crystal plane of bulk silicon from alower limit of about 1°, 2°, or 3°, or 4° to an upper limit of about 8°,7°, 6°, 5°, or 4°. The shift may range from any lower limit to any upperlimit and encompass any subset therebetween.

Unless otherwise specified, the terms “SiGeNC” and “GeNC” encompass bothunstrained and strained structures thereof. Further, as describedherein, the SiGeNC and GeNC having the various properties and/orcharacteristics described herein (e.g., 20 value shift, averagediameter, and the like) may be used to produce Li—SiGeNC and Li—GeNC,respectively. As such, it should be understood that the properties ofthe SiGeNC and GeNC described herein may extend to the Li—SiGeNC andLi—GeNC described herein.

In some embodiments, the SiGeNC described herein may comprise a moleratio of silicon to germanium that ranges from a lower limit of about1:10, 1:5, or 1:1 to an upper limit of about 10:1, 5:1, or 1:1, andwherein the mole ratio may range from any lower limit to any upper limitand encompasses any subset therebetween.

In some embodiments, the SiNC, SiGeNC, and/or GeNC described herein maybe p-doped or n-doped. In some embodiments, the SiGeNC may be in a“core-shell” configuration with a germanium lattice core surrounded by asilicon lattice shell. In some embodiments, the SiGeNC may merely be acombination or mixture of separate SiNCs and GeNCs.

In some embodiments, the SiNC, SiGeNC, and/or GeNC described herein mayhave an average diameter in at least one dimension ranging from a lowerlimit of about 3 nm, 5 nm, 10 nm, 25 nm, or 100 nm to an upper limit ofabout 1000 nm, 500 nm, 250 nm, 150 nm, 100 nm, or 50 nm. The averagediameter in at least one dimension may range from any lower limit to anyupper limit and encompasses any subset therebetween. In particular, SiNCmay be under 150 nm diameter and preferably under 50 nm. Germaniumnanocrystals may be under 1000 nm in diameter and preferably under 100nm. Above these diameters the, nanocrystals may not maintain long rangeorder after several lithiation-dilithiation cycles and the materialsbecome amorphous.

In some embodiments, the SiNC, SiGeNC, and/or GeNC described herein mayhave a narrow diameter distribution such that the standard deviationfrom the average diameter ranges from a lower limit of ± about 0.5 nm, 1nm, or 2 nm to an upper limit of ± about 10 nm, 7 nm, or 5 nm. Thestandard deviation may range from any lower limit to any upper limit andencompasses any subset therebetween.

In some embodiments, the SiNC, SiGeNC, and/or GeNC described herein mayhave a multimodal diameter distribution (e.g., bimodal, trimodal, and soon). It is desirable to have a range of sizes from as-small-as-possibleto the upper limits of SiNC and GeNC noted above in order to increasethe packing density of the nanocrystals on a conducting anode substrateand thus maximize the diffusion density of lithium ions within andbetween the nanocrystals. An example of a self-organizing bimodaldistribution 800 of two different sizes of germanium nanocrystals isdepicted in the micrograph of FIG. 8. As shown, the larger-sizednanocrystals 802 (e.g., 50 nm diameter) arrange to form a base layer ona substrate while the smaller-sized nanocrystals 804 (e.g., 12 nmdiameter) arrange in the spacing between the larger-sized nanocrystals802. In this way, the density of the nanocrystals is increased.

In exemplary embodiments, the SiGeNC and/or GeNC described herein havinga multimodal diameter distribution may have at least one mode with anaverage diameter in at least one dimension ranging from a lower limit ofabout 4 nm, 7 nm, 12 nm, or 25 nm to an upper limit of about 250 nm, 150nm, 100 nm, or 50 nm. The average diameter in at least one dimension mayrange from any lower limit to any upper limit and encompasses any subsettherebetween. In some embodiments, the modes of a multimodal diameterdistribution of the SiNC, SiGeNC, and/or GeNC described herein mayindependently have a narrow diameter distribution such that the standarddeviation for each mode independently ranges from a lower limit of ±about 0.5 nm, 1 nm, or 2 nm to an upper limit of ± about 10 nm, 7 nm, or5 nm. The standard deviation may range from any lower limit to any upperlimit and encompasses any subset therebetween.

In some embodiments, the Li—SiGeNC and Li—GeNC described herein may havea mole ratio of Li to SiGe (i.e., the combined moles of Si and Ge) or Lito Ge, respectively, ranging from a lower limit of greater than 0, about0.2, 0.5, 1, 1.5, or 2 to an upper limit of about 3.6, 3.5, 3.25, 3,2.5, 2, or 1.5. The mole ratio of Li to SiGe or Li to Ge may range fromany lower limit to any upper limit and encompasses any subsettherebetween. It should be noted that such mole ratios are described interms of a fully charged battery or other similar device. The mole ratioof Li to SiGe or Li to Ge may depend on, inter alia, the ratio of thelithium source to the SiGeNC and/or GeNC in the synthesis of theLi—SiGeNC and/or Li—GeNC.

In some embodiments, lithium intercalation may be effected at least oneof: mixing the SiGeNC and/or GeNC with lithium metal (e.g., folding thetwo together and allowing the lithium to intercalate), mixing the SiGeNCand/or GeNC with lithium metal in the presence of an ionic liquid,electrodepositing the SiGeNC and/or GeNC on lithium metal electrode, andthe like. In some embodiments, the ionic liquid and electrodepositionmay be used in combination.

In some exemplary implementations, elemental lithium from a lithiummetal electrode intercalates into the SiNC, SiGeNC, and/or GeNCattracted to the surface thereof such that a paste of lithiatednanocrystals and ionic liquid forms on the lithium metal electrode. Thepaste has a dark-brown to purple-black color depending on the amount oflithium present. It has been observed that the paste of Li—SiGeNC and/orLi—GeNC is stable in air for extended periods of time and may be exposedto water without reaction unlike lithium metal. The intercalation of thelithium ions within the nanocrystal structures protects the lithium frominteraction with air and moisture. Further, in the case of GeNCs,germanium does not form surface oxides in air like silicon, whichfurther improves the diffusion speed of lithium ions.

Once formed, the lithiated nanocrystal paste may be used in furtheranode manufacturing processes without need for a protective environment(e.g., an argon-filled enclosure), which can significantly reduce thecost and difficulty of the process. Further, the nonvolatile paste mayadvantageously enable batteries and similar devices with minimal to norisk of fire in the event of battery damage that exposes the anode toair or water. Such an advantage and risk mitigation may be exploited inthe production of lighter-weight batteries because the battery casingsmay be made of different materials, which may be useful in electricvehicles where much of the battery weight can be attributed toprotection from puncture in crashes.

In some embodiments, the anode may comprise a conductive support havinga film disposed thereon, the film comprising the nanocrystals describedherein. Examples of the conductive supports may include, but are notlimited to, silicon, germanium, graphite, nickel, iron, stainless steel,aluminum, copper, and the like, and any combination thereof. In someembodiments, the conductive support may be in a form that is at leastone of the following: a sheet, a foil, a grid, a rod, and the like, andany hybrid thereof, which may, inter alia, depend on the configurationof the battery or other device in which the anode is to be used.

In some embodiments, the film may consist essentially of thenanocrystals described herein. In other embodiments, the film maycomprise the nanocrystals described herein and optionally furthercomprise binders and/or existing anode materials. These optionalcomponents may be used to achieve the desired physical characteristicsof the film and/or the precursor thereof. Examples of physicalcharacteristics may include, but are not limited to, the rheology of thefilm precursor, the drying characteristics of the film precursor, thefilm plasticity, the film conductivity, the adhesion strength of thefilm to the conductive support, and the like, and any combinationthereof.

In some embodiments, binders may be useful in achieving the desiredphysical characteristics of an anode film or precursor thereof byadhering the nanocrystals together or to a conductive support. Thebinders may minimally, if at all, impact the electrochemistry of theresultant battery or similar device in which the anode is used. Bindersmay be conductive or insulating. Examples of binders may include, butare not limited to, polyvinylidene fluoride, N-methyl-2-pyrrolidone,carboxymethyl cellulose, agar, styrene-butadiene rubber,polytetrafluoroethylene, conductive acetylene black, conductive graphitepowders, and the like, and any combination thereof. In some embodiments,the binder may be selected to enable a hydrogel or organogel film (e.g.,crosslinked agar or carboxymethyl cellulose). In some embodiments, thebinder may be selected to enable a printable film precursor that drieslike ink (e.g., conductive graphite powder). In some embodiments, thebinder may be selected to enable a flexible, dry film (e.g.,styrene-butadiene rubber or polytetrafluoroethylene).

Existing anode materials may be useful in achieving the desired physicalcharacteristics of the film or precursor thereof and may participate inthe electrochemistry of the resultant battery or similar device in whichthe anode is used. In some embodiments, the use of existing anodematerials may be minimized or eliminated because they provide little tono enhancement to the anode properties and occupy volume that couldotherwise be filled by nanocrystals described herein. Examples ofexisting anode materials may include, but are not limited to, graphitepowder, carbon microbeads, Li₄Ti₅O₁₂, LiVPO₄F, and the like, and anycombination thereof.

The concentration of the various components in the film precursor may beat levels necessary to achieve the desired physical characteristics ofthe film and/or the precursor thereof and the desired electrochemicalcharacteristics of the anode, which may allow for each of the componentconcentration to vary between about 0% and about 99% by weight of thefilm precursor.

In some embodiments, the film precursor may be a paste. For example, afilm precursor may be the paste described above that is produced duringat least some embodiments of the synthesis of Li—SiNC, Li—SiGeNC, and/orLi—GeNC. In another example, a paste film precursor may be a paste ofSiGeNC, graphite, and polyvinylidene fluoride in N-methyl-2-pyrrolidone.In some embodiments, the anode may comprise a fast ion conductor layer(e.g., lithium nitride or the like) between the conductive support andthe film.

In some embodiments, the film precursor may be a less viscous liquid,which may be a diluted paste or formed independently. In someembodiments, lower viscosities may be achieved with the use of organicsolvents (e.g., benzene, methanol, and the like). In some embodiments,the film precursor may be at a viscosity that enables deposition ontothe conductive substrate by methods like electrodeposition, spraying,painting, dip coating, calendaring, and the like. Such methods mayadvantageously enable scaling the production of anodes described hereinto industrial production levels, e.g., using coating methods similar tothat used in the semiconductor industry or using printing methods inproducing flexible batteries or similar devices.

In some embodiments, after deposition onto a conductive substrate, thefilm precursor may be dried to yield the film that comprises thepre-lithiated nanocrystals described herein (e.g., between about 30° C.and about 220° C. depending on the composition of the film precursor).In some embodiments, after deposition onto the conductive substrate, thefilm precursor may be allowed to set to yield a hydrogel or organogelfilm that comprises the pre-lithiated nanocrystals described herein.

The diffusion limit of lithium into a SiNC, SiGeNC, or GeNC depositioncoating is typically between 30-40 microns. Therefore, in someembodiments, the thickness of the film comprising the nanoparticlesdescribed herein may have a thickness ranging from a lower limit ofabout 10 microns, 25 microns, or 100 microns to an upper limit of about500 microns, 250 microns, or 100 microns. The thickness may range fromany lower limit to any upper limit and encompasses any subsettherebetween.

FIG. 9 is a flowchart depicting a general electrodeposition process 900for preparing a pre-lithiated nanocrystal paste for use in anodeconstruction. In step 902, SiNCs, SiGeNCs, and/or GeNCs are mixed into asolution of an ionic fluid(s), a nonaqueous solvent(s), or a combinationof both to form a colloidal suspension of the nanocrystals. A lithiummetal ribbon is positioned in the colloidal mixture as an anodeelectrode as indicated in step 904. Similarly, a carbon electrode isplaced into the colloidal mixture as a cathode as provided in step 906.A voltage is then applied across the anode and cathode to drive thenanocrystals from the mixture to coalesce on the lithium metal ribbonanode as indicated in step 908. Lithium ions from the lithium metalintercalate into the nanocrystals deposited on the lithium metal and thelithiated nanocrystals in the presence of the ionic fluid and/or solventform a paste on the surface of the lithium metal ribbon. Thelithium-diffused nanocrystal paste is then removed from the lithiummetal anode as indicate in step 910. Finally, a prelithiated anode isformed by spreading or otherwise distributing the paste over anelectrode, such as a fast ion conductor or a solid electrolyte, asindicated in step 912.

FIG. 10 is a flowchart depicting a general electrolytic process 1000 forpreparing a pre-lithiated nanocrystal paste for use in anodeconstruction. In step 1002, SiNCs, SiGeNCs, and/or GeNCs are mixed intoa solution of an ionic fluid(s), a nonaqueous solvent(s), or acombination of both, plus a lithium electrolyte, to form a colloidalsuspension of the nanocrystals. A first piece of lithium metal ribbon isconnected to a positive electrode as provided in step 1004 and a secondpiece of lithium metal ribbon is connected to a negative electrode asprovided in step 1006. Each of the first and second pieces of lithiummetal is positioned in the colloidal mixture as indicated in step 1008with care taken to ensure physical separation of the lithium metalelectrodes as noted in step 1010. A voltage is then applied across theelectrodes to drive the nanocrystals from the mixture to coalesce on thelithium metal ribbon anode as indicated in step 1012. The voltage ismaintained until lithium ions from the lithium metal ribbon intercalateinto the deposited nanocrystals and a paste of lithiated nanocrystalsand solvent forms on the surface of the lithium metal ribbon as providedin step 1014. The voltage source is then disconnected from theelectrodes and the lithium-diffused nanocrystal paste is removed fromthe lithium metal ribbon as indicated in step 1016. The paste is thenmixed with binder and/or conductive carbon under ambient conditions,i.e., in air at atmospheric pressure without additional safeguards suchas an inert gas or low moisture environment, as indicated in step 1018.The paste and binder mixture is then spread or otherwise distributed ona conductive anode substrate as provided in step 1020. Finally, thebinder is cured in order to adhere the lithiated nanocrystal paste tothe anode substrate to complete formation of a prelithiated anode asindicated in step 1022.

Example 1: Anode Construction Via Electrodeposition

In accordance with the general method shown in FIG. 9 and describedabove, a high-energy capacity anode for lithium ion batteries may beformed via electrochemical super saturation of lithium into silicon,germanium, and silicon-germanium alloy nanoparticles. Silicon,germanium, and/or silicon-germanium alloy nanoparticles (UniversalNanotech Corporation), were suspended as a colloid in a mixture of anionic fluid 1-butyl-3-methylimidazolium thiocyanate (bmimSCN) and anon-aqueous solvent dimethylacetamide. A ⅔″ strip of Li metal ribbon wasused as an anode and carbon electrode was used as a cathode. Each wasconnected to a respective terminal of a voltage source and placed in thecolloidal mixture. Voltage in a range of 250 mV-5 V, typically 2-4V, wasapplied to drive a current through the solution to begin the Liintercalation into the nanocrystals.

The nanocrystals are driven to the Li metal anode. Visually, the lithiumribbon appears to “swell” and take on a reddish-orange-maroon color.This “swelling” is a coating of the lithiated nanocrystals on thedecomposed lithium ribbon. The final consistency of the resultingproduct is a paste or gel-like consistency with lubricity provided bythe ionic fluid/solvent mixture. An anode was formed by spreading thegel with a spatula over a sheet comprised of a fast ion conductor (e.g.,solid electrolyte, such as lithium nitride. The nanocrystal anode pasteon the fast ion conductor structure was then sandwiched on top of acathode material (LiMn2O4). An aluminum electrode was attached to thecathode (i.e., LiMn2O4) and a copper electrode was attached to the anodeto form a battery. The entire structure was sealed in a protectivenonconductive lamination sheet with portions of the aluminum and copperelectrodes protruding outside the lamination sheet to serve as terminalsfor the battery.

Example 2: SiGeNC Lithiation Using Ionic Fluid bmimSCN

In an argon filled environment (i.e., a glove box), two separate piecesof lithium metal foil (each 2 cm L×1 cm W×0.038 cm t) were connected,respectively, to the negative and positive electrodes of a power supply.Si0.22Ge0.78NCs were dispersed into 1-butyl-3-methylimidazoliumthiocyanate (bmimSCN) and heated to 40° C. under argon with constantstirring in an Erlenmeyer flask. The concentration of Si0.22Ge0.78NCs inthe ionic fluid was matched to the lithium (1 cm L×1 cm W×0.038 cm t)such that nearly all the lithium was absorbed by the amount of GeNCscontained in the flask. For this experiment, 0.00288 mol Li (1 cm²) and0.0160 mol of Si0.22Ge0.78NCs were used. The electrodes were placeddirectly opposed to each other 1 cm apart with 1 cm² of the Li metalsubmerged into the Si0.22Ge0.78NCs-ionic fluid dispersion. A constantvoltage 3V was used to drive the Si0.22Ge0.78NCs to the lithium metal onthe positive electrode where the lithium subsequently diffused into theSi0.22Ge0.78NCs. The reaction was stopped after 25 minutes. Theresultant product was a deep red paste comprised of the ionic fluid andlithiated Si0.22Ge0.78NCs.

Example 3: Anode Construction Using Electrolyte LiTFSI

The process of Example 2 was altered to introduce an electrolyte,lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to make a 1Msolution of LiTFSI in bmimSCN. The general method was thus changed tofollow the process shown in FIG. 10 and described above. Additionally,the process was conducted at room temperature. In all other respects theconditions were the same. The addition of the lithium salt (LiTFSI)reduced the reaction time to create the paste from 25 minutes to 15minutes.

Example 4: Anode Construction Using Electrolyte LiPF₆

In accordance with the general method shown in FIG. 10 and describedabove, in an argon filled environment (e.g., in a glove box) at roomtemperature and atmospheric pressure, two separate pieces of lithiummetal foil (each 2 cm L×1 cm W×0.038 cm t) were connected, respectively,to the negative and positive electrodes of a power supply. High quality(spherically symmetric) germanium nanocrystals (<150 nm diameter) weredispersed into an electrolyte of lithium salt, i.e., lithiumhexafluorophosphate (LiPF₆) in a 1:1 ratio of ethylene carbonate todiethyl carbonate in an Erlenmeyer flask. The electrodes were placeddirectly opposed to each other 1 cm apart with 1 cm² of the Li metalsubmerged into the GeNC-electrolyte dispersion. For this experiment,0.00288 mol LiPF₆ and 0.0127 mol of GeNCs were used. The concentrationof germanium nanocrystals in the electrolyte was matched to the lithium(1 cm L×1 cm W×0.038 cm t) such that nearly all the lithium is absorbedby the amount of germanium contained in the flask. A constant voltage 4Vwas used to drive the germanium nanocrystals to the lithium metal on thepositive electrode where the lithium diffused into the GeNCs depositedonto the lithium foil. The reaction was stopped after 15 minutes. Theresultant product was a viscous dark purple-black paste comprised ofelectrolyte and lithiated GeNCs. The paste can then be mixed with abinder or conductive carbon additive and be deposited onto a conductivesubstrate for use as a lithium-ion battery anode.

Example 5: Anode Construction Using bmimSCN with Electrolyte LiPF₆

The process of Example 4 was altered to use 1-butyl-3-methylimidazoliumthiocyanate (bmimSCN) as the ionic fluid in conjunction with lithiumhexaflurophosphate LiPF6). In other respects the apparatus, conditions,and techniques of Example 4 remained the same with the exception of alower voltage of between 2V-4V held constant while the electrochemicalreaction occurred. A dark brown to purple black paste comprised ofelectrolyte and lithium loaded GeNCs formed on the lithium electrode. Ananode was formed with the paste and it was combined with a cathodeelectrode in a manner similar to Example 1 to form a cell. FIG. 11depicts a series of discharge/recharge cycles 1100 for this exemplarycell. The cell was tested for energy capacity and volumetric energydensity according to standard Li-ion battery testing protocol. Eachcharge cycle 1102 had a charge rate of C/10 and a discharge rate of 1 C.The cell had a 98% Coulomb efficiency, i.e., each discharge cycle 1104was consistently 98% of energy that was put in for the charge.

Example 6: Half-cell Anode Constructed from Lithiated NanocrystalMaterial

Germanium nanocrystals were mixed into a slurry with poly acrylic acidbinder (PAA)-450, Super-P Li conductive additive (Timcal), andN-Methyl-pyrollidone. The ratio of Li—GeNC to conductive carbon tobinder was 40:40:20. The mixture was bath sonicated for 15 minutes andthen spread with a doctor blade onto a copper foil current collector.The slurry coated copper electrode was then placed in an oven at 60° C.to evaporate the solvent (N-Methyl-2-pyrollidone). After drying, thecoated copper electrode was calendered (roll pressed) to achieve a filmthickness of 10 μm. Discs with a diameter of 11 mm were punched out ofthe paste coated copper electrode for half-cell assembly. The resultingmass loading was measured to be 2.98 mg/cm2 of Li—GeNC.

The half-cell was assembled in an argon filled glove box using a 2032stainless steel coin cell with a negative base and positive cap. Aschematic diagram of the components of the half-cell anode 1200 in anexploded view is depicted in FIG. 12 and a method 1300 for assemblingthe half-cell is presented in FIG. 13. Initially, 25 μL of electrolyte1204 is deposited at the center of the cell case base 1202 as indicatedin step 1302. In this example, the electrolyte is 1M LiPF6 influoroethylene carbonate (FEC) (both from Aldrich) (<0.1 ppm O2). Next,the Cu/Li—GeNC anode 1206 is placed onto the electrolyte droplet 1204 inthe center of the base 1202 with the anode Li—GeNC paste-coated side upand Cu side down as indicated in step 1304. Another 25 μL of electrolyte1208 is then added to the center of the anode 1206 as indicated in step1306. A 19 mm diameter polypropylene separator 1210 (e.g., Celgard 2500membrane separator at 25 μm thickness), sized to cover the entire cellbase 1202, was placed onto the anode 1206 as indicated in step 1308.Another 25 μL of electrolyte 1212 was then deposited on the center ofthe separator 1210 as indicated in step 1310. A second polypropyleneseparator 1214 (also commensurate in size with the cell base 1202) wasplaced onto the first separator 1210 over the electrolyte 1212 asindicated in step 1312. A further 25 μL of electrolyte 1216 was thenadded to the center of the second separator 1314.

A lithium foil disk 1218 of at least the same diameter as the anode 1206was placed onto the center of the second separator 1214 to act as acounter/reference electrode as indicated in step 1316. A stack of twostainless steel spacers 1220, 1222 centered on the cell base 1202 wereplaced onto the lithium foil disk 1218 as indicated in step 1318. Abiasing device such as a spring washer 1224 was placed onto the spacerstack 1220, 1222 as indicated in step 1320. The cell cap 1226 is thenplaced over the spring washer 1224 as indicated in step 1322 and thecell cap 1226 and cell base 1202 are compressed together to encase theother components of the cell stack as indicated in step 1324. (Anyexcess electrolyte forced out when cell is compressed may be wiped off.)The cell cap 1226 and cell base 1202 may then be sealed together asindicated in step 1326, for example, by placing the half-cell 1200 in acrimping tool with the cell base 1202 oriented downward and crimping andremoving any excess fluid after crimping. The half-cell anode 1200 maybe used to make a full coin cell as described in further detail belowwith respect to FIGS. 15 and 16.

Once the half-cell 1200 was completed, an initial conditioning cycle ofC/20 using 1 C=1180 mAh/g and constant current for charge-discharge wasrun between 0.01 V and 1V vs. Li/Li+. Subsequent cycles were carried outat a rate of 1 C. FIG. 14 shows a graph 1400 of two sequential chargecycles 1402 a/b and related discharge cycles 1404 a/b for the GeNC anodehalf-cell 1200 of Example 6. Each of the charge cycles 1402 a/b reachesa specific energy capacity of about 1080 mAh/g from an original capacityof 1100 mAh/g after multiple recharge cycles, thus indicating nobreakdown in the charge capacity of the anode as the nanocrystals expandand contract with lithiation and dilithiation.

Example 7: Anode Cycle Testing

A plurality of samples were prepared by electrodepositing GeNC on toglass coated with indium tin oxide. Using an Agilent Technologies 4155CSemiconductor Parameter Analyzer and two Alessi needle probes in contactwith the sample, I-V curves were obtained, and V_(OC) values of about 7to about 14 were measured. Further, the charge-discharge rates observedwere comparable to other technologies like bulk silicon or germanium.

Batteries and Similar Devices Comprising the Disclosed Cathodes andAnodes

In some embodiments, batteries and similar devices described herein maycomprise an anode described herein that comprises the nanocrystalsdescribed herein; a cathode; a separator disposed between the cathodeand the anode; and an electrolyte. One skilled in the art with thebenefit of this disclosure should understand the plurality ofconfigurations for such components to achieve a desired the battery andsimilar device. Examples of similar devices may include, but are notlimited to, super-capacitors, ultra-capacitors, capacitors, dual in-linepackage batteries, flex batteries, large-format batteries, and the like.

Examples of cathode materials may, in some embodiments, include, but arenot limited to, lithium cobalt oxide, lithium nickel oxide, lithiummanganese oxide, lithium iron phosphate, lithium cobalt nickel manganeseoxide, polypyrrole, polyaniline, and the like, and any combinationthereof.

Examples of separators may, in some embodiments, include, but are notlimited to, polyolefin-based separators, fluorinated polyolefin-basedseparators, fluorine resin based separators (e.g., polyethyleneseparators), polypropylene separators, polyvinylidene fluorideseparators, VDF-HFP copolymer separators, polyethylene/polypropylenebilayer separators, polypropylene/polyethylene/polypropylene triplelayer separators, polyethylene/polypropylene/polyethylene triple layerseparators, and the like, any hybrid thereof, and any combinationthereof.

In some embodiments, the electrolyte of the half-cells, batteries, andsimilar devices described herein may be a traditional electrolyte, e.g.,a lithium salt in a non-aqueous solvent optionally with a polymer or asolid electrolyte. Examples of lithium salts may include, but are notlimited to, fluorine-containing inorganic lithium salts (e.g., lithiumbis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF₆, and LiBF₄),chlorine-containing inorganic lithium salts (e.g., LiClO₄),fluorine-containing organic lithium salts (e.g., LiN(CF₃SO₂)₂,LiN(C₂F₅SO₂)₂, LiCF₃SO₃, LiC(CF₃SO₂)₃, LiPF₄(CF₃)₂, LiPF₄(C₂F₆)₂,LiPF₄(CF₄SO₂)₂, LiPF₄(C₂F₅SO₂)₂, LiBF₂(CF₃)₂, LiBF₂(C₂F₅)₂,LiBF₂(CF₃SO₂)₂, and LiBF₂(C₂F₅SO₂)₂), and the like, and any combinationthereof. Examples of non-aqueous solvents may, in some embodiments,include, but are not limited to, 1-butyl-3-methylimidazolium thiocyanate(bmimSCN), N-butyl-N-methylpyrrolidiniumbis(trifluoromethanesulfonyl)imide (Pyr14TFSI), cyclic carbonates (e.g.,ethylene carbonate and propylene carbonate), linear carbonates (e.g.,dimethyl carbonate and ethylmethyl carbonate), cyclic carboxylic acidesters (e.g., γ-butyrolactone and γ-valerolactone), and the like, andany combination thereof. Examples of solid electrolytes may include, butare not limited to, polyethylene oxide (PEO), polyacrylnitrile (PAN), orpolymethylmethacrylate (PMMA), and the like, and any combinationthereof. Examples of solid electrolytes (also known as fast ionconductors) may, in some embodiments, include, but are not limited to,lithium nitride, lithium iodide, lithium phosphate, and the like, andany combination thereof.

In some embodiments, the use of the nanocrystals described herein mayenable the production of batteries and similar devices that can becycled (i.e., charged and discharged) a plurality of times (e.g., about500 times or greater) with minimal power density loss.

In some embodiments, the use of the nanocrystals described herein mayenable the production of batteries and similar devices that have atailorable open circuit voltage (V_(OC)), which may range from about 0.1V to about 18 V including any subset therebetween. The V_(oc) of thedevice may depend on, inter alia, the morphology and composition of thenanocrystals. Advantageously the V_(OC) values that can be achieved beadvantageous in producing higher voltage devices as bulk silicon andgermanium have V_(OC) levels on the order of about 0.4 V to about 1.1 V.

Example 8: Battery Cell with Li—GeNC Anode

A battery prototype was produced using an anode comprising Li—GeNCs. Theanode measured an energy density per area of about 7.67 mWh/cm² and acapacity per area of about 2.32 mAh/cm², which were used to derive theanode energy density of about 38,350 Wh/L, an anode specific energy of13,456 Wh/kg, and an anode specific capacity of about 3,684 Ah/kg.Further, upon several charge-discharge cycles (greater than 20), thebattery showed no measurable degradation in performance. Such a batteryhas been charged and retained the charge for two to three weeks with nomeasurable loss of charge.

Example 9: Battery Cell with Li—SiGeNC Anode

Another battery prototype was produced using an anode comprising lithiumstored in SiGeNCs. The anode measured an energy density per area ofabout 3 mAh/cm². Further, upon several charge-discharge cycles (greaterthan 20), the battery showed no measurable degradation in performance.Such a battery has been charged and retained the charge for two to threeweeks with no measurable loss of charge.

Example 10: Full Coin Cell Battery with Li—SiGeNC Anode and S—C NanotubeCathode

FIG. 15 is a schematic view of full coin cell, generally designated1500. FIG. 16 is a method, generally designated 1600 for assembling afull coin cell in accordance with the embodiment of FIG. 15. The fullcoin cell may include a cell base 1502, a half-cell cathode 1504, one ormore separators 1506 a/b, a half-cell anode 1508, one or more spacers1510 a/b, a biasing device 1512, and a cell cover 1514.

In step 1602, an electrolyte 1516 a is provided to the cell base 1502.The electrolyte 1516 a may be, for example, 0.25 E⁻³ mol g⁻¹ of LiNO₃(LiNO₃=68.95 g mol⁻¹), 0.25 E³ mol g⁻¹ of DEMMOX (DEMMOX=466.4 g mol⁻¹),and a 1:1 (wt.) mixture of DME and DOL. In one embodiment, 25 μL of theelectrolyte 1516 a is provided to the center of the cell base 1502. Instep 1604, the half-cell cathode 1504 is placed into the electrolyte1516 a. In various embodiments, the half-cell cathode 1504 includes asulfur charged carbon nanotube cathode as described above with respectto FIGS. 1-6. In various embodiments, the cathode 1504 is placed withthe aluminum contact of the cathode 1504 toward the cell base 1502 andthe sulfur charged carbon nanotube coated side away from the cell base1502. In step 1606, additional electrolyte 1516 b is provided on top ofthe half-cell cathode 1504. In one embodiment 25 μL of the electrolyte1516 b is provided on top of the half-cell cathode 1504.

In step 1608, a first separator 1506 a is placed on top of theelectrolyte solution and the cathode 1504. In various embodiments, thefirst separator 1506 a may have a diameter commensurate with thediameter of the cathode 1504. In certain embodiments, the firstseparator 1506 a may be a 19 mm polypropylene separator. In step 1610,additional electrolyte 1516 c is provided on top of the first separator1506 a. In one embodiment 25 μL of the electrolyte 1516 c is provided ontop of the first separator 1506 a. In step 1612, a second separator 1506b is placed on top of the electrolyte solution 1516 c and the firstseparator 1506 a. In various embodiments, the second separator 1506 bmay have a diameter commensurate with the diameter of the firstseparator 1506 a. In certain embodiments, the second separator 1506 bmay be a 19 mm polypropylene separator. In step 1614, additionalelectrolyte 1516 d is provided on top of the second separator 1506 b. Inone embodiment 25 μL of the electrolyte 1516 d is provided on top of thesecond separator 1506 b.

In step 1616, a half-cell anode 1508, that is at least as large as thecathode diameter, is centered and placed on the electrolyte 1516 d onthe second separator 1506 b. In various embodiments, the half-cell anode1508 may completely cover the cathode 1504. In certain embodiments, thehalf-cell anode 1508 may be produced as described above with respect toFIGS. 12 and 13. In step 1618, the one or more spacers 1510 a/b areplaced on top of the half-cell anode 1508. In various embodiments, thespacers 1510 a/b may be stainless steel spacers. In various embodiments,two spacers 1510 a/b are placed on the half-cell anode 1508. In step1620, the biasing device 1512 is placed on top of the spacers 1510 a/b.In various embodiments, the biasing device 1512 may be a spring washer.In other embodiments, the biasing device 1512 may be any other type ofbiasing device that does not interfere with the electrical properties ofthe full coin cell 1500. In step 1622, the cell cover 1514 is placedover the cell base 1502 to enclose the contents of the full coin cell1500. In various embodiments, enclosing the full coin cell 1500 maycause electrolyte to leak from the full coin cell 1500. Any electrolytemay be removed from the outside of the full coin cell 1500. In step1624, the cell cover 1514 and the cell base 1502 are sealed together tocreate a complete full coin cell 1500.

Production of High Quality and Strained Nanocrystals

The methods and systems of the present disclosure may advantageouslyenable the high-yield production of nanoparticles (e.g., 85% or greateryield in some embodiments), and especially nanocrystals and metalnanoparticles, with narrow size distributions (e.g., ± about 2 nm insome embodiments). Further, the methods and systems described herein arecapable of being adapted to relatively high-production rates (e.g.,kilograms per hour) and continuous methods, which may enableindustrial-scale production of highly uniform nanoparticles, includingnanocrystals and metal nanoparticles. As used herein, the term“nanoparticle” is interchangeable with the term “nanocrystal” and shouldbe understood as such for those elements that form crystallinestructures.

In addition, the methods and systems described herein have beenunexpectedly found to, in some embodiments, yield unique nanoparticlecompositions, which may be useful in a plurality of applicationsincluding ion batteries and quantum energy devices.

Various embodiments described herein may involve producing nanoparticlesby heating an aerosolized precursor solution, which in some embodimentsmay be adapted for continuous and high-production rate nanoparticleproduction.

Some embodiments may involve aerosolizing a precursor solution in thepresence of a flowing carrier gas, thereby yielding a reactant stream;heating the reactant stream to form a product stream that comprises aplurality of nanoparticles; cooling the product stream; and passing theproduct stream through a liquid to collect the nanoparticles from theproduct stream. In some embodiments, the precursor solution may comprisea volatile solvent and nanoparticle precursors; and the reactant streammay be heated to a temperature above the boiling point of the volatilesolvent. As used herein, the term “nanoparticle” refers to particleshaving at least one dimension less than about 40 μm and encompassesamorphous nanoparticles, nanocrystals, core-shell nanoparticles,non-spherical nanoparticles (e.g., oblong or rod-like particles),substantially spherical nanoparticles, hollow spherical nanoparticles,and the like.

Aerosolizing the precursor solution forms droplets that, when heatedabove the boiling point of the volatile solvent, may cause the volatilesolvent to evaporate from the droplet and the nanoparticle precursorsdroplets to coalesce and react, thereby yielding nanoparticles, and insome instances nanocrystals. It should be noted that depending on theconditions of synthesis (e.g., aerosolizing parameters, reactiontemperatures, volatile solvent composition, and nanoparticle precursorcompositions and/or concentrations) nanoparticles may be formed by a onedroplet-one nanoparticle mechanism, a ripening mechanism, adisintegration mechanism, or a combination thereof. In variousembodiments, the one droplet-one nanoparticle mechanism may producemonodispersed particles (i.e., single size particles). In otherembodiments, the disintegration mechanism may produce bimodal, trimodal,or other multi-modal nanoparticle size distributions. Such multimodaldistributions of nanoparticles may enable higher packing efficiency whendeposited in a layer on a substrate.

Referring now to FIG. 17, a system for producing nanoparticles,generally designated 1700, is shown. The system 1700 may include aprecursor solution vessel 1710 that contains a precursor solution 1712,which has submersed therein a sonicator 1714 for producing an aerosol B.The sonicator 1714 may be attached to a control box 1716 that enablesmanipulation of the frequency, amplitude, and waveform produced by thesonicator 1714. Further, the precursor solution vessel 1710 has acarrier gas A passing though it, which mixes with the aerosol B to yielda reactant stream C. The reactant stream C may pass through a reactionzone 1718 where the reactant stream C is heated by heaters 1720 a,b and1722 a,b to yield a product stream D comprising nanoparticles. Theheaters 1720 a,b and 1722 a,b may be adjusted to form different zones inthe reaction zone C having different zone temperatures. The productstream D is then passed through a collection liquid 1728 in a collectionvessel 1726 where the nanoparticles are at least substantially removedfrom the product stream D to yield an effluent stream E. As shown here,three-way valves 1724 and 1730 are used to control the pressure and gasflow rates through the collection vessel 1726 so as to prevent thecollection liquid 1728 from flowing back into the reaction zone 1718. Itshould be noted that other mechanism like vacuum and additional carriergases introduced above the reaction zone may also be utilized to assistin preventing the collection liquid 1728 from flowing back into thereaction zone 1718.

In some embodiments, precursor solutions may comprise a volatile solventand a nanoparticle precursor. Volatile solvents may, in someembodiments, be organic solvents having a boiling point of about 300° C.or less. Examples of volatile solvents suitable for use in conjunctionwith the methods described herein may include, but are not limited toalcohols (e.g., methanol, ethanol, isopropanol, and butanol), glycols,acetonitrile, water, and the like, any derivative thereof, and anycombination thereof. Anhydrous precursor solvents may be used tominimize oxidation of the final product. The solvent may be selected,for example, based on the dielectric constant of the solvent. In variousembodiments, the dielectric constant of the solvent may be matched tothe dielectric constant of organometallic precursors. In otherembodiments, the solvent may be selected based on its miscibility. Forexample, in certain embodiments, it may be desirable to create anemulsion for use as precursor as opposed to solvents miscible withprecursor that creates a solution.

Nanoparticle precursors may, in some embodiments, be organometalliccompounds. Nanoparticle precursors may include silicon chloride,germanium chloride, etc. Nanoparticle precursors may comprisestransition elements (e.g., titanium, chromium, iron, cobalt, nickel,copper, zinc, molybdenum, palladium, silver, cadmium, tungsten,platinum, and gold), lanthanide elements (e.g., europium, gadolinium,and erbium), Group III elements (boron, aluminum, gallium, indium, andthallium), Group IV elements (e.g., germanium, silicon, tin, lead, andcarbon), Group V elements (e.g., nitrogen, phosphorous, arsenic,antimony, and bismuth), Group VI elements (e.g., oxygen, sulfur,selenium, and tellurium), or any combination thereof. Examples ofnanoparticles precursors suitable for use in conjunction with themethods described herein may, in some embodiments, include, but are notlimited to, tetraethylgermane, tetramethylgermane, tetraethylsilane,tetramethylsilane, diethylsilane, diethylgermane, diethyl silane,tetrapropyl germane, tetrapropyl silane and the like, any derivativethereof, or any combination thereof.

In some embodiments, more than one nanoparticle precursor may beutilized in the precursor solutions described herein. For example, aprecursor solution may comprise a first nanoparticle precursor thatincludes germanium and a second nanoparticle precursor that includessilicon. In some embodiments, precursor solutions may comprise more thanone nanoparticle precursor such that the mole ratio of the metal of thefirst nanoparticle precursor (e.g., germanium) to the metal of thesecond nanoparticle precursor (e.g., silicon) ranges from a lower limitof about 1:10, 1:5, or 1:1 to an upper limit of about 10:1, 5:1, or 1:1,and wherein the mole ratio may range from any lower limit to any upperlimit and encompasses any subset therebetween. In other embodiments,when multimodal distributions are desired, pure organometallicprecursors may be used in accordance with a droplet disintegrationmechanism. One skilled in the art with the benefit of this disclosureshould understand that the germanium and silicon example is nonlimitingand other combinations of nanoparticle precursors may be applicable,e.g., cadmium and selenium, tin and tellurium, and zinc and sulfur.

In some embodiments, the nanoparticle precursors may be present in theprecursor solutions described herein in an amount ranging from a lowerlimit of about 20%, 30%, 40%, or 50% by volume of the precursor solutionto an upper limit of about 90%, 70%, 50%, or 40% by volume of theprecursor solution, and wherein the amount may range from any lowerlimit to any upper limit and encompasses any subset therebetween.

In some embodiments, aerosolizing the precursor solution may involve atleast one of sonicating the precursor solution with the sonication probeimmersed in the precursor solution (e.g., as shown in FIG. 17),nebulizing the precursor solution, passing the precursor solutionthrough a nozzle (e.g., an aerosolizing nozzle), electrostaticprecipitation, and the like, and any combination thereof.

In some embodiments, aerosolizing the precursor solution, including byany method described herein, may be performed at a frequency rangingfrom a lower limit of about 1 kHz, 10 kHz, 100 kHz, 1 MHz, 10 MHz, or100 MHz to an upper limit of about 1000 MHz, 100 MHz, 10 MHz, 1 MHz, or100 kHz, and wherein the frequency may range from any lower limit to anyupper limit and encompasses any subset therebetween (e.g., 3 kHz to 150kHz). In some embodiments, aerosolizing the precursor solution,including by any method described herein, may be performed at afrequency so as to yield strained nanoparticles (described furtherherein), which may be a frequency ranging from a lower limit of about 1kHz, 3 kHz, 10 kHz, or 15 kHz to an upper limit of about 200 kHz, 150kHz, 50 kHz, or 25 kHz, and wherein the frequency may range from anylower limit to any upper limit and encompasses any subset therebetween,e.g., 5 kHz to 22 kHz.

In some embodiments, aerosolizing the precursor solution, including byany method described herein, may be performed at an input power rangingfrom a lower limit of about 10 Watts (or a frequency of about 5 kHz) toan upper limit of about 100 Watts (or a frequency of about 22 kHz), andwherein the input power may range from any lower limit to any upperlimit and encompasses any subset therebetween. Those skilled in the artwill appreciate that additional factors relating to energy supplied tothe system may also affect the physical properties of the resultingnanoparticles, such as the internal strain. Additional factors mayinclude waveform, amplitude, heat, or any other additional energy addedinto the system when forming droplets at input.

In some embodiments, the aerosolized precursor solution B may be mixedwith a carrier gas A to form a reactant stream C. The carrier gas A maytransport the aerosolized precursor solution through the reaction zone1718. Further the flow rate of the carrier gas A may be adjusted toprovide for a desired residence time of the reactant stream C in thereaction zone 1718. In some embodiments, the residence time of thereactant stream C in the reaction zone 1718 may range from a lower limitof about 1 sec to an upper limit of about 10 sec.

In some embodiments, the carrier gas A may be an inert gas (e.g.,helium). In other embodiments, the carrier gas A may not be inert (e.g.,hydrogen). Examples of carrier gases suitable for use in conjunctionwith the methods described herein may, in some embodiments, include, butare not limited to, hydrogen, helium, nitrogen, argon, carbon dioxide,and the like, and any combination thereof.

In some embodiments, the reactant stream C may be heated to atemperature above the boiling point of the volatile solvent so as toform a product stream D that comprises a plurality of nanoparticles. Insome embodiments, the temperature above the boiling point of thevolatile solvent may range from a lower limit of about 500° C., 600° C.,or 700° C. to an upper limit of about 1200° C., 1100° C., 1000° C., or900° C., and wherein the temperature may range from any lower limit toany upper limit and encompasses any subset therebetween.

In some embodiments, heating may involve passing the reactant stream Cthrough a tube furnace, series of tube furnaces, or the like. Withoutbeing limited by theory, it is believed that nanoparticle precursorsand/or nanoparticles may collect on the walls of the tube passingthrough the tube furnace, thereby decreasing the overall yield ofnanoparticles produced. Various embodiments may minimize interactionbetween the walls and the reactant stream. Minimizing such interactionsmay, in some embodiments, involve at least one of orienting the tubefurnace vertically, spinning the tube through which the reactant streamis passing, applying an electric charge to the tube, providing sheathflow within the tube furnace (e.g., flowing a sheath of a gas betweenthe tube wall and the reactant stream), creating a vortex within thereactant stream (e.g., with a spinning or oscillating rod or the likeextending into the reaction zone), using a tapered tube in conjunctionwith a cortex, and the like, any hybrid thereof, and any combinationthereof.

Some embodiments may pass the product stream D through the collectionliquid 1728 so as to collect the nanoparticles therein. The collectionliquid 1728 may, in some embodiments, be solvents suitable for use inapplications downstream of nanoparticle production (e.g., deposition onsurfaces, compounding with polymers, chemical modification, and thelike). Examples of the collection liquid 1728 suitable for use incollecting nanoparticles produced by the methods and systems describedherein may include methanol, ethanol, glycol, water, tetrahydrofuran(THF), diethylcarbonate, acetonitrile, dichlorobenzene, acetone,toluene, pentane and the like, any derivative thereof, or anycombination thereof.

In some embodiments, the collection liquid 1728 may further comprisesuspension agents, which may, in some embodiments, assistant suspensionof the nanoparticles and/or mitigate clustering of the nanoparticles. Insome embodiments, suspension aids may covalently or noncovalentlyinteract with the nanoparticles. Examples of suspension agents suitablefor use in conjunction with the production of nanoparticles describedherein may include surfactants, polymers, chelating agents, cappingagents (e.g., octanol, oleylamine, and trioctylamine), and the like, orany combination thereof.

In some embodiments, the path that the product stream C follows from thereaction zone to the collection liquid 1728 may be substantiallystraight (e.g., containing a bend or deviation of about 30° or less)and/or substantially vertical (e.g., about 30° or less off-vertical) tominimize the collection of nanoparticle precursors and/or nanoparticleson surfaces, thereby increasing the yield of nanoparticles. In someembodiments, the yield of nanoparticles may be about 65% or greater,about 75% or greater, or more preferably about 85% or greater (e.g.,about 85% to about 90%) by weight of the metal of the nanoparticleprecursor relative to the metal of the nanoparticle produced.

In some embodiments, the methods and systems described herein may beadapted for continuous and high-production rate nanoparticle production.Referring now to FIG. 18, a system for producing nanoparticles,generally designated 1800, is shown. The system 1800 may includeprecursor solution vessel 1810 that contains precursor solution 1812.The precursor solution 1812 may be in contact with an apparatus 1814,e.g., a large-scale mister or fogger, capable of producing large volumesof aerosolized precursor solution B. To enable a continuous process,system 1800 may include syringe pump 1832 (or another similar automatedaddition system) for continuous addition of precursor solution 1812.

Precursor solution vessel 1810 has passing through it a carrier gas A,which mixes with an aerosol B to yield a reactant stream C. The reactantstream C may pass through a reaction zone 1818 where the reactant streamC is heated by heaters 1820 a/b to yield a product stream D thatcomprises nanoparticles. It should be noted that the reaction zone 218may comprise a single large diameter tube or the like as illustrated inFIG. 18 or several smaller tubes or the like in parallel to accommodatethe larger processing volumes associated with the use of the solutionvessel 1812. The product stream D is then passed through a collectionliquid 1828 in a collection vessel 1826 where the nanoparticles are atleast substantially removed from the product stream D to yield aneffluent stream E. As shown, the collection vessel 1826 may comprise aninlet 1834 and an outlet 1836 for continuous flow of the collectionliquid 1828 to enable continuous extraction of the nanoparticlesproduced in this or a similar process.

As used herein, the term “continuous” refers to being withoutinterruption for a prolonged time frame (e.g., about 3 hours orgreater). It should be noted that continuous actions may be performedintermittently over the short-term (e.g., seconds to minutes) and stillbe considered continuous over the long term. For example, continuousaddition of precursor solutions may include the intermittent addition ofprecursor solutions over a prolonged time frame, e.g., the addition ofabout 1 mL of precursor solution every 15 minutes.

Some embodiments may continuously aerosolize a precursor solution 1812in the presence of a flowing carrier gas A, thereby yielding a reactantstream C; continuously replenishing the precursor solution 1812; heatingthe reactant stream C to a temperature above a boiling point of thevolatile solvent so as to form a product stream D that comprises aplurality of nanoparticles; cooling the product stream D; and passingthe product stream D through a collection liquid 1828 so as to collectthe nanoparticles from the product stream.

Some embodiments may further involve continuously replacing thecollection liquid 1828, e.g., when the nanoparticles have reached adesired concentration therein.

Some embodiments may further involve extracting the nanoparticles fromthe collection liquid 1828 (e.g., continuously or batchwise). In someembodiments, extracting the nanoparticles from the collection liquid1828 may involve centrifuging, continuous centrifuging (e.g., flowcentrifugation), filtering, concentrating the nanoparticles, decantingthe collection liquid after having allowed the nanoparticles to settle,and the like, and any hybrid thereof.

In some embodiments, the methods and systems described herein may formunstrained nanoparticles and/or strained nanoparticles. For example, ina bimodal distribution larger nanoparticles may form having strain,while smaller nanoparticles may have negligible strain. As used herein,the term “strained nanoparticles” refers to nanoparticles having astrained crystal structure, which can be determined by a shift in acrystal plane when analyzed by x-ray diffraction (“XRD”). In someembodiments, the strained nanoparticles may be nanocrystals, core-shellnanoparticles with a crystalline core and an amorphous shell, SiGe coreshell nanoparticles, and the like. It should be noted that, unlessotherwise specified, the term “nanoparticle” encompasses both unstrainednanoparticles and strained nanoparticles.

Without being limited by theory, it is believed that the frequency ofaerosolization, the amplitude of aerosolization, residence time in thereaction zone, and temperature affect the degree of strain, diameterdistribution, and/or the morphology of the nanoparticle formed by thesystems and processes described herein. For example, the use of higherfrequencies during aerosolization may yield larger nanoparticles. Inanother example, the use of higher amplitudes during aerosolization mayyield nanoparticles with higher strain.

The nanoparticles (strained or unstrained) may comprise the metal(s) ofthe nanoparticle precursor(s) used in the production of thenanoparticles. For example, the methods and systems described herein mayutilize a precursor solution comprising cadmium and selenium may yieldcadmium selenide nanoparticles. In another example, the methods andsystems described herein may utilize a precursor solution comprisinggold, platinum, or palladium to yield gold, platinum, or palladiumnanoparticles. In yet another example, methods and systems describedherein may utilize a precursor solution comprising germanium and siliconin a desired ratio so as to yield nanoparticles comprising germanium andsilicon at about the desired ratio.

Strained nanoparticles may, in some embodiments, comprise Group III,Group IV, Group V, and/or Group VI elements. For example, a strainedsilicon nanoparticle may have a 2θ value for the (111) crystal planeshifted by about 4° to about 6° from the (111) crystal plane of bulksilicon. In some embodiments, the 2θ value for the (111) crystal planeof the strained nanoparticles may shift relative to the correspondingbulk material from a lower limit of about 1°, 2°, or 3°, or 4° to anupper limit of about 8°, 7°, 6°, 5°, or 4°, and where the shift mayrange from any lower limit to any upper limit and encompasses any subsettherebetween.

In some embodiments, the strained nanoparticles may comprise Group IVelements (e.g., germanium, silicon, tin, lead, carbon, or anycombination thereof). In other embodiments, the strained nanoparticlesmay comprise a mole ratio of silicon to germanium that ranges from alower limit of about 1:10, 1:5, or 1:1 to an upper limit of about 10:1,5:1, or 1:1, and wherein the mole ratio may range from any lower limitto any upper limit and encompasses any subset therebetween.

In some embodiments, the nanoparticles (strained or unstrained)described herein may have an average diameter in at least one dimensionranging from a lower limit of about 3 nm, 5 nm, 10 nm, 25 nm, or 100 nmto an upper limit of about 1000 nm, 500 nm, 250 nm, 150 nm, 100 nm, or50 nm, and wherein the average diameter in at least one dimension mayrange from any lower limit to any upper limit and encompasses any subsettherebetween.

In some embodiments, the nanoparticles (strained or unstrained)described herein may have a narrow diameter distribution such that thestandard deviation from the average diameter ranges from a lower limitof ± about 0.5 nm, 1 nm, or 2 nm to an upper limit of ± about 10 nm, 7nm, or 5 nm, and wherein the standard deviation may range from any lowerlimit to any upper limit and encompasses any subset therebetween.

In some embodiments, the nanoparticles (strained or unstrained)described herein may have a multimodal diameter distribution (e.g.,bimodal, trimodal, and so on). In some embodiments, the nanoparticles(strained or unstrained) described herein having a multimodal diameterdistribution may have at least one mode with an average diameter in atleast one dimension ranging from a lower limit of about 4 nm, 7 nm, 12nm, or 25 nm, to an upper limit of about 250 nm, 150 nm, 100 nm, or 50nm, and wherein the average diameter in at least one dimension may rangefrom any lower limit to any upper limit and encompasses any subsettherebetween.

In some embodiments, the modes of a multimodal diameter distribution ofthe nanoparticles (strained or unstrained) described herein mayindependently have a narrow diameter distribution such that the standarddeviation for each mode independently ranges from a lower limit of ±about 0.5 nm, 1 nm, or 2 nm to an upper limit of ± about 10 nm, 7 nm, or5 nm, and wherein the standard deviation may range from any lower limitto any upper limit and encompasses any subset therebetween.

In some embodiments, the nanoparticles may produce photoluminescencebased on the size of the nanoparticles. When the physical size of aparticle is less than its exciton radius (i.e., physical distance anelectron must travel from its valence band to conduction band), thequantum phenomenon of photoluminescence can be observed. For example,the exciton radius of silicon is 24 nm. That is, an electron must travel24 nm from its valence band to the conduction band. However, variousembodiments may produce silicon particles that are less than 24 nm,(e.g., it is possible to synthesize 5 nm silicon particles). In suchembodiments, when a photon of sufficient energy (i.e., ultraviolet lightor, more specifically, a photon greater than the band gap energy of thenanoscale material) is absorbed by the nanoparticle, an electron isexcited from the valence band to the conduction band. The electron maythen fall back into the valence band and emit a photon of light at awavelength based on the difference between the particle size and theexciton radius. In the case of 5 nm silicon, it is blue light. As thephysical size of the particle approaches the exciton radius,photoluminescence is no longer observed and the material begins tobehave as a bulk material.

In various embodiments, the diameter of the nanoparticles may bedetermined based on the relationshipD_(p)=σ*(f)^(−0.66)(Q)^(0.207)(Y)^(−0.11)(ρ)^(0.274)(η)^(0.166)(power/area)^(0.4)where Dp is the diameter of the resulting particles, σ is a constantwhich depends on temperature and choice of precursor solution, f is thetransducer/sonicating frequency, Q is the flow rate of the carrier gas,Y is the surface tension of the precursor, ρ is the density of theprecursor, η is viscosity of the precursor, and power/area is the powerdensity.

In some embodiments, the strained nanoparticles may exhibitpiezoelectric effects. Piezoelectricity is the special circumstance ofelectrical charge build-up that arises in certain solid materialstructures due to mechanical stress. Generally, the piezoelectric effecthas been experimentally determined to be a linear electromechanicalinteraction between the mechanical and the electrical state incrystalline materials with no inversion symmetry. The piezoelectriceffect is a reversible process such that the internal generation ofelectrical charge resulting from an applied mechanical force can bereversed with the internal generation of a mechanical strain resultingfrom an applied electrical field.

Regarding the piezoelectric effect in bulk semiconductors, changes ininteratomic spacing resulting from strain affects the semiconductorsintrinsic band gap making it easier (or harder depending on the materialand strain) for electrons to be raised into the conduction band. Thepiezoelectric effect of semiconductor materials can be several orders ofmagnitudes larger than the analogous geometrical effect in metals and ispresent in materials like germanium, polycrystalline silicon, amorphoussilicon, silicon carbide, and single crystal silicon.

The piezoelectric effects of semiconductors have been used for sensordevices with a variety of semiconductor materials such as germanium,polycrystalline silicon, amorphous silicon, and single crystal silicon.Since silicon is currently the material of choice for nearly allintegrated circuits, the use of piezoelectric silicon devices has beenan intense area of research interest.

Regarding the piezoresistive effect in bulk single crystal silicon andgermanium, the resistance of silicon and germanium can change due to astress-induced change of geometry, but also due to the stress dependentresistivity of the material. The resistance of n type silicon(predominant charge carriers responsible for electrical conduction areelectrons) mainly changes due to a shift of the three differentconducting vertices of the crystal. The shifting causes a redistributionof the carriers between vertices with different mobilities. This resultsin varying mobilities dependent on the direction of current flow. Aminor effect is due to the effective mass change related to shapedistortion due to change in the inter-atomic spacing of valley verticesin single crystal silicon. In p-type silicon (predominant chargecarriers responsible for electrical conduction are holes) the phenomenacurrently being researched are more complex and also demonstrate changesin mass and hole transfer.

Regarding the piezoelectric mechanism, the nature of the piezoelectriceffect is rooted in the occurrence of electric dipole moments in solids.An electric dipole moment is a vector quantity equal to the product ofthe magnitude of charge and the distance of separation between thecharges. Electric dipole moments in solids may either be induced forions on crystal lattice sites as in an asymmetric charge environmentsuch as in lithium tantalate and lead zirconate-titanate or may bedirectly carried by molecular groups such as in organic sugar molecules.The dipole density causing polarization is the sum of the dipole momentsper unit volume of a crystal unit cell. Since electric dipoles arevector quantities (geometric objects of specific magnitude anddirection), the dipole density P is also a vector quantity. Dipoles neareach other tend to be aligned in regions called Weiss domains. In thesealigned regions occurring between individual particles, the particlesact as a whole. Thus, the potential and polarity of voltage andmagnitude and direction of the current is equal to the sum of allindividual particles making up the entire solid.

To reiterate, typically the piezoelectric effect occurs with an appliedmechanical stress but can also be manifested by manufacturing internalstress into certain solids. Piezoelectricity arises because of variationof the polarization strength, direction, or both. The magnitude anddirection of the charge depends on the interrelationships between theorientation of its dipole density P within individual particles,particle symmetry, and the applied mechanical stress or induced internalstress. Although the change in an individual crystal's dipole densityappears quantitatively as a variation of surface charge density upon theindividual crystal faces, the overall useful energy arising from thepiezoelectric phenomenon is caused by the superposition of the dipoledensities of the crystals that make up the entire piece of material,i.e., as a sum of the individual crystallographic unit cells that makeup a whole crystal. For example, a 1 cm³ cube of quartz with 500 lb ofmechanically applied force at the right point can produce a voltage ofabout 12500 V because the resultant force is the sum of all theindividual crystallographic unit cells that make up the whole crystal.

Regarding power generation in bulk polar crystal structures synthesizedin a state of stress, there are 32 crystal classes that represent 32possible combinations of symmetry operations in crystalline materials.Each crystal class includes crystal faces that uniquely define thesymmetry of the class. Of the thirty-two crystal classes, twenty-one arenon-centrosymmetric (not having a centre of symmetry), and of these,twenty exhibit direct piezoelectricity. Ten of these include the polarcrystal classes, which show a spontaneous polarization without anapplied mechanical stress due to a non-vanishing electric dipole momentassociated with asymmetry inherent in their crystal structure. For polarcrystals, for which the summation of the dipole density P≠0 holdswithout applying a mechanical load, the piezoelectric effect manifestsitself by changing the magnitude or the direction of P or both. Statedanother way, polar crystals that can be manufactured to have internalstress will demonstrate a piezoelectric effect without an appliedmechanical load.

Restated another way, for non-polar piezoelectric crystals, an appliedmechanical load transforms the material from a non-polar crystal class(P=0) to a polar one, having P≠0 and hence gives rise to a voltagepotential and useful energy capable of powering an external device.However, crystals predisposed to an internal state of stress have aninherent polar structure for which P≠0 and hence energy can bedischarged from the structure without an applied mechanical load. Duringdischarge of electrical energy, the crystal relaxes back into itspreferred state of interatomic spacing.

In various embodiments, producing strained nanocrystals depends on avariety of factors including, for example, the composition of thenanocrystals, the temperature(s) of the reaction zone(s), the frequencyand power of the sonicator/mister/fogger/transducer, among otherfactors. In one embodiment, strained Si nanocrystals may be produced ina three stage reaction zone, where the three stages have temperatures of850° C., 850° C., and 650° C., and the power supplied by the sonicatoris greater than 175 W and less than 700 W. In another embodiment,strained germanium nanocrystals may be produced in a three stagereaction zone, where the three stages have temperatures of 750° C., 750°C., and 550° C., and the power supplied by the sonicator is greater than462 W and less then 700 W. In yet another embodiment, SiGe nanocrystalsmay be produced in a three stage reaction zone, where the three stageshave temperatures of 800° C., 800° C., and 575° C., and the powersupplied by the sonicator is greater than 390 W and less than 700 W.

In addition to producing strained nanoparticles, various embodimentsenable production of quantum confined nanoparticles, which allows forincreased energy density in a quantum energy device (QED) produced withthe nanoparticles. Quantum confinement in nanocrystals occurs when thephysical size of the particle is less than its characteristic excitonBohr radius. The exciton Bohr radius is the physical distance separatinga negatively charged electron from its positively charged hole leftbehind during excitation. When the physical size of the particle is lessthan the distance the electron must travel during excitation, thematerial is considered to be quantum confined. For example, the excitonBohr radius for germanium is 24.3 nm; however, it is possible tosynthesize germanium nanocrystals to be 1 nanometer in diameter. Bycreating nanoparticles smaller than this characteristic distance, theelectronic properties of the nanoparticles can be tuned to discreetenergy levels by adjusting particle size. Thus, an aggregate made ofparticles smaller than the Bohr radius will enjoy a greatly increasedenergy density. If the particles are about the same size as the Bohrexciton radius, or even a little larger, an aggregate of the particleswill still enjoy increased energy density, if not to the same degree asif all of the particles were smaller than the exciton Bohr radius.

Nanoparticles produced according to embodiments of this disclosure alsobenefit from shallow potential wells and therefore require lessactivation energy than larger particles to excite electrons from thevalence band to the conduction band by virtue of quantum tunneling.Potential wells are a direct result of synthesizing physical particledimensions to be smaller than their respective exciton Bohr radius. Apotential well is the region surrounding a local minimum of potentialenergy in nanomaterials. Energy captured in a potential well is unableto convert to another type of energy because it is captured in the localminimum of the potential well. Therefore, a body may not proceed to theglobal minimum of potential energy, as it naturally would, according tothe universal nature of entropy. Energy may be released from a potentialwell if sufficient energy is added to the system such that the localminimum energy for excitation is sufficiently overcome. However, inquantum physics potential energy may escape a potential well withoutadded energy due to the probabilistic characteristics of quantumparticles. In these cases, a particle may be imagined to tunnel throughthe walls of a potential well without energy added to the system.

FIG. 19 illustrates a method of producing a nanoparticle coating or film1910 on a substrate 1915 under conditions of ambient atmosphericcomposition and pressure. The embodiment of FIG. 19 may also beperformed at ambient or slightly elevated temperature. The embodiment ofFIG. 19 includes electrophoretically depositing nanoparticles 1925 froma nonaqueous colloidal suspension 1930 and substantially uniformlydepositing 1935 the nanoparticles 1925 onto the substrate 1915. Thecoating or film 1910 may, in some embodiments, be less than 1000nanometers in thickness, but may be thicker in other embodiments. Asubstrate 1915 desired to be coated may be prepared by first cleaning1940 the substrate 1915, and then, if the substrate 1915 is notsufficiently electrically conductive, coating 1943 the substrate 1915with a layer of conductive material 1945, such as silver or indium tinoxide (typically used to prepare optical elements, since thin layers ofindium tin oxide are substantially optically transparent).

A nonaqueous suspension 1930 of nanoparticles 1925 may be prepared orprovided from the synthesis of the nanoparticles (e.g., thenanoparticles in the collection liquid as described herein), for use inthe deposition process. The liquid suspension medium 350 (or collectionliquid depending on the embodiment) may be a polar solvent, such as2-butanol, 1,2-dichlorobenzene and/or acetone, or the like. The liquidsuspension medium 350 composition is selected taking into account suchproperties as its inherent dielectric constant, Hamaker constant,miscibility, viscosity, and the like. In various embodiments, a blend ofaprotic polar nonaqueous solvents 1955 and protic polar nonaqueoussolvents 1960 is selected to define the liquid suspension medium 1950.

In some embodiments, small amounts of an ionic liquid 1965, such as1-butyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide may beadded to the liquid suspension medium 1950 (or collection liquiddepending on the embodiment) to facilitate deposition of nanoparticlefilms 1910.

In some embodiments, a buffer solution (not shown) may be added to theliquid suspension medium 1950 (or collection liquid depending on theembodiment) to manage the surface charge on the nanoparticles 1925. Forexample, silicon particles are negatively charged in the pH rangebetween about 6 and about 9 while germanium particles are negativelycharged in the pH range from about 3 to about 5.

Regarding preparing a nanoparticle suspension, a predetermined andmeasured amount of nanoparticles 1925 may be dispersed in the liquidsuspension medium 1950 (optionally including the ionic liquid 1965and/or a buffer solution (not shown)). The liquid suspension medium 1950may be agitated until the nanoparticles 1925 are generally evenly andhomogeneously dispersed to define a colloidal suspension 1930.

The substrate 1915 connected to a DC power source 1970 may serve as acathode 1975 while a second electrode or electrode array 1980 (such as acarbon electrode) immersed the colloidal suspension 1930 may be used tocomplete an electric circuit and establish an electric field. Thesubstrate 1915 is typically the cathode 1975 and the carbon electrode istypically the anode 1980. The electrodes/electrode arrays 1975, 1980 maybe, for example, maintained at a distance of between about 0.5 and about4.0 centimeters apart, depending upon such variables as the desireddeposition pattern, the shape of the electrodes 1975, 1980, the shape ofthe substrate 1915, and the like. However, under certain circumstancesthe electrode separation distance may fall outside of the 0.5 to 4.0centimeter range. The applied voltage is typically between about 3 andabout 12 volts, depending on the nanoparticle size. The nanoparticles1925 in the colloidal suspension 1930 electrophoretically migrate to thesubstrate 1915, forming a substantially even coating 1910 thereupon.

The nanoparticles 1925 may, in some embodiments, be of any convenientshape and geometry, and are generally regularly shaped and are typicallyblocky, and, more typically, generally spherical. Typically, thenanoparticles 1925 will be tightly sized, having a relatively narrowdiameter distribution, to yield a coating or film 1910 of nanoparticles1925 having a narrow diameter distribution, such as, for example,wherein most of the nanoparticles 1925 fall in the 3-10 nanometer range.Alternately, the applied voltage, current and/or the pH of the colloidalsuspension 1930 may be varied to yield similar control over the size ofthe deposited nanoparticles 1925 when the colloidal suspension 1930includes a substantial amount of nanoparticles 1925 falling outside thetarget size range. Further, by varying the applied voltage and/or the pHof the colloidal suspension 1930, multiple layers of nanocrystals may beapplied to a substrate 1915 in a predetermined, size-specific ofgraduated order. The deposition process 1935 may be continued until thedesired film thickness is achieved, typically for about 30 seconds toabout 5 minutes to yield a deposited layer typically from a few hundredto a few thousand nanometers thick. Typically, the deposition process1935 is conducted under ambient atmosphere; no vacuum is required.

The effective surface area of the film 1910 is a function of thenanocrystalline particle size and shape and is governed by the desiredend use and does not change the method of deposition. Likewise, there isno requirement that the electrode or electrode array 1980 be of equal orlarger size than the cathode 1975 that the nanoparticles will bedeposited upon.

Once electrophoretic deposition 1935 of the nanoparticles 1925 iscomplete, a coated substrate 1985 may be finished by depositing a metalcontact 1990 via thermal evaporation or the like over the film 1910 toprotect the nanoparticle film 1910 and establish a pathway for electronsto travel to be used to power an external device. The metal contact 1990is typically a highly electrically conductive metal, such as gold,platinum, silver, copper or the like, and is typically, but not limitedto, between about 100 nm and about 400 nm thick.

Using standard electrical connection techniques, multiple coatedsubstrates 85 may be connected in a series/parallel fashion to yield aquantum energy device 1900 configured to generate the desiredvoltage/current supply configuration. In some embodiments, a QED can becompleted and configured to power a desired load.

Example 11

Strained silicon nanoparticles were produced in a reactor similar tothat described above in reference to FIG. 1 in the verticalconfiguration so illustrated. Tetraethylsilane and methanol were mixedto yield a precursor solution. The precursor solution was sonicated withan QSONICA MODEL Q700 sonicator (available from QSONICA) immersedtherein at a frequency of about 22 kHz. An argon carrier gas flowing atabout 1000 mL/min was used to transport the aerosolized precursorsolution into the reaction zone (approximately 1 m in length), which wasat about 850° C. The product stream was collected in methanol. Theresultant nanoparticles were analyzed by transmission electronmicroscopy and x-ray diffraction.

Example 12

Strained silicon nanoparticles were produced in a reactor similar tothat described above in reference to FIG. 17 in the verticalconfiguration so illustrated. Isobutylsilane was used as a precursorsolution. The precursor solution was sonicated with an QSONICA MODELQ700 sonicator (available from QSONICA) immersed therein at a frequencyof about 20 kHz. A carrier gas flowing at about 16.67 cm³/s was used totransport the aerosolized precursor solution into the reaction zone(approximately 1 m in length), which was divided in to three zoneshaving temperatures of about 850° C., 850° C., and 650° C.,respectively. The product stream was then collected. The resultantnanoparticles were approximately 12 nm in diameter with a σ value of0.00165 and a strain of approximately +0.45 degrees in the 111 plane ofthe silicon crystal as determined by transmission electron microscopyand x-ray diffraction.

Example 13

Strained germanium nanoparticles were produced in a reactor similar tothat described above in reference to FIG. 17 in the verticalconfiguration so illustrated. Tetraethylgermane was used as a precursorsolution. The precursor solution was sonicated with an QSONICA MODELQ700 sonicator (available from QSONICA) immersed therein at a frequencyof about 20 kHz. A carrier gas flowing at about 16.67 cm³/s was used totransport the aerosolized precursor solution into the reaction zone(approximately 1 m in length), which was divided in to three zoneshaving temperatures of about 750° C., 750° C., and 550° C.,respectively. The product stream was then collected. The resultantnanoparticles were approximately 8 nm in diameter with a σ value of0.00142 and a strain of approximately +1.4 degrees in the 111 plane ofthe silicon crystal as determined by transmission electron microscopyand x-ray diffraction.

Example 14

Strained silicon-germanium nanoparticles were produced in a reactorsimilar to that described above in reference to FIG. 17 in the verticalconfiguration so illustrated. Isobutylsilane and tetraethylgermane ereused as a precursor solution. The precursor solution was sonicated withan QSONICA MODEL Q700 sonicator (available from QSONICA) immersedtherein at a frequency of about 20 kHz. A carrier gas flowing at about16.67 cm³/s was used to transport the aerosolized precursor solutioninto the reaction zone (approximately 1 m in length), which was dividedin to three zones having temperatures of about 800° C., 800° C., and575° C., respectively. The product stream was then collected. Theresultant nanoparticles were produced in a ratio of approximately 1:3silicon to germanium with a σ value of 0.00149 and a strain ofapproximately +1.64 degrees in the 111 plane of the silicon crystal asdetermined by transmission electron microscopy and x-ray diffraction.

The particular embodiments disclosed above are illustrative only, andmay be modified and practiced in different but equivalent mannersapparent in view of the teachings herein. Furthermore, no limitations tothe details of construction or design herein shown are intended, otherthan as described in the claims below. It is therefore evident that theparticular illustrative embodiments disclosed above may be altered,combined, or modified and all such variations are considered within thescope and spirit of the present invention. The invention illustrativelydisclosed herein suitably may be practiced in the absence of any elementthat is not specifically disclosed herein and/or any optional elementdisclosed herein. All numbers and ranges disclosed above may vary bysome amount. Whenever a numerical range with a lower limit and an upperlimit is disclosed, any number and any included range falling within therange is specifically disclosed. In particular, every range of values(of the form, “from about a to about b,” or, equivalently, “fromapproximately a to b,” or, equivalently, “from approximately a-b”)disclosed herein is to be understood to set forth every number and rangeencompassed within the broader range of values.

The above specification, examples and data provide a completedescription of the structures, methods, and use of exemplary embodimentsof the invention as defined in the claims. Although various embodimentsof the claimed invention have been described above with a certain degreeof particularity, or with reference to one or more individualembodiments, those skilled in the art could make numerous alterations tothe disclosed embodiments without departing from the spirit or scope ofthe claimed invention. Other embodiments are therefore contemplated. Itis intended that all matter contained in the above description and shownin the accompanying drawings shall be interpreted as illustrative onlyof particular embodiments and not limiting. Changes in detail orstructure may be made without departing from the basic elements of theinvention as defined in the following claims.

What is claimed is:
 1. A method for manufacturing anodes for use in alithium ion battery comprising mixing Si, Ge, or SiGe nanocrystalswithin a fluid containing a lithium electrolyte; placing a first lithiummetal electrode within the fluid mixture placing a second lithium metalelectrode within the fluid mixture spatially separated from the firstlithium metal electrode; applying a voltage across the electrodes suchthat the first lithium metal electrode is positively charged; andallowing a paste of lithium-intercalated Si, Ge, or SiGe nanocrystalssuitable for use in a prelithiated anode of a lithium ion battery toform on the first lithium metal electrode.
 2. The method of claim 1,further comprising removing the paste from the first lithium metalelectrode; and mixing the paste with a binder.
 3. The method of claim 2further comprising mixing the paste with a conductive carbon additive.4. The method of claim 2 further comprising depositing the paste andbinder mixture on a conductive anode substrate; and curing the binder toadhere the paste to the conductive anode substrate.
 5. The method ofclaim 4, wherein the depositing and curing operations are conductedunder ambient temperature and pressure conditions in air.
 6. The methodof claim 1, wherein the Si nanocrystals are substantially spherical andare 150 nm or less in diameter.
 7. The method of claim 1, wherein the Genanocrystals are substantially spherical and are 150 nm or less indiameter.
 8. The method of claim 1, wherein the fluid contains an ionicfluid, a nonaqueous solvent, or a combination of both.
 9. The method ofclaim 8 further comprising removing the paste from the first lithiummetal electrode; and mixing the paste with a binder.
 10. The method ofclaim 9 further comprising mixing the paste with a conductive carbonadditive.
 11. The method of claim 9 further comprising depositing thepaste and binder mixture on a conductive anode substrate; and curing thebinder to adhere the paste to the conductive anode substrate.
 12. Themethod of claim 11, wherein the depositing and curing operations areconducted under ambient temperature and pressure conditions in air. 13.The method of claim 8, wherein the Si nanocrystals are substantiallyspherical and are 150 nm or less in diameter.
 14. The method of claim 8,wherein the Ge nanocrystals are substantially spherical and are 150 nmor less in diameter.